CN112778721A - Preparation method of high-toughness hydrolysis-resistant PLA material and packaging box - Google Patents
Preparation method of high-toughness hydrolysis-resistant PLA material and packaging box Download PDFInfo
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- CN112778721A CN112778721A CN202011614686.5A CN202011614686A CN112778721A CN 112778721 A CN112778721 A CN 112778721A CN 202011614686 A CN202011614686 A CN 202011614686A CN 112778721 A CN112778721 A CN 112778721A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention provides a preparation method and a packaging box of a high-toughness hydrolysis-resistant PLA material, wherein the preparation method adopts the following raw materials in parts by weight: 60-65 parts of polylactic acid (PLA), 20-25 parts of at least one of flexible degradable plastics PBAT, PBS or PES, 8-10 parts of an inorganic compatilizer, 2-3 parts of a chain extender and 2-3 parts of a plasticizer, and the PLA material is prepared by a blending system. The toughness, mechanical strength and hydrolysis resistance of the PLA material prepared by the preparation method are obviously improved, and further the practical application value of the PLA material is improved. The packaging box material is the PLA material obtained by the preparation method, and has good toughness and hydrolysis resistance; meanwhile, the material of the packaging box is degradable, and meets the requirement of environmental protection.
Description
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a preparation method and a packaging box of a high-toughness hydrolysis-resistant PLA material.
Background
Polylactic acid (PLA) is one of the most widely used environment-friendly materials at present, has good biocompatibility and biodegradability, can be completely degraded into water and carbon dioxide under the action of microorganisms and enzymes, and is widely applied to a plurality of fields such as packaging, medical use, 3D printing and the like.
But current PLA articles also suffer from non-negligible drawbacks. Because PLA is a polyester material and the relative molecular mass is uneven, the heat resistance and the impact strength of the material are poor, and the actual production requirements are difficult to meet. And a large number of ester bonds are contained on the PLA chain segment, the PLA chain segment is easy to be broken into hydroxyl and carboxyl under the action of water molecules in the air, and the carboxyl generated after the breakage can further promote the hydrolysis of the PLA to form an autocatalysis circulation system, so that the degradation speed of the PLA is accelerated.
The characteristics of no toxicity, no carcinogenic effect, easy degradation and good biocompatibility of PLA meet related requirements and are popular, but in the field of packaging with the most extensive application of PLA, the characteristics of easy hydrolysis and poor toughness of PLA are adverse factors, the external packaging of various commodities needs longer storage time and mechanical property retention time, the mechanical property of the commodities is reduced due to the excessively fast hydrolysis speed of PLA, the service life of the commodities is shortened, the quality guarantee period and the shelf life of the commodities are shortened, and the tensile property and the impact resistance of a common PLA material are not good, so that the further popularization of PLA is seriously hindered due to the defect.
Disclosure of Invention
Aiming at the easy hydrolyzability and poor stretchability of common PLA materials, the toughness and hydrolysis resistance of PLA are enhanced by adding other flexible degradable plastics, chain extenders and plasticizers, so that the practical application value of the PLA material is improved.
A preparation method of a high-toughness hydrolysis-resistant PLA material comprises the following raw materials in parts by weight: 60-65 parts of polylactic acid (PLA), 20-25 parts of at least one of flexible degradable plastics PBAT, PBS or PES, 8-10 parts of an inorganic compatilizer, 2-3 parts of a chain extender and 2-3 parts of a plasticizer;
the preparation method comprises the following steps:
drying treatment of raw materials A:
drying at least one of polylactic acid PLA and PBAT, PBS or PES in an oven at 70-80 ℃ for 8h, exhausting air once every 4h, sealing the dried granules for later use,
drying the inorganic compatilizer in a vacuum oven at 60 ℃ for 8 hours, exhausting air in the oven every 4 hours, sealing the dried powder for later use,
drying the chain extender in a vacuum oven at 40 ℃ for 8 hours, exhausting the air in the oven every 4 hours, and sealing for later use after drying;
b, preparation of a blending system:
compounding 60-65 parts of polylactic acid (PLA), 20-25 parts of PBS, 8-10 parts of an inorganic compatilizer, 2-3 parts of a chain extender and 2-3 parts of a plasticizer, and performing melt blending processing by using a double-screw extruder, wherein the set rotating speed of the double-screw extruder is 75-80r/min, the double-screw extruder is provided with a plurality of heating intervals, the temperature of the adjacent heating intervals is increased or leveled along the material extrusion direction, the temperature of the heating intervals is 160-185 ℃, and the temperature of a discharging machine head of the double-screw extruder is 185 ℃;
c, injection molding: and injection molding the melt-blended extruded melt by an injection molding machine, wherein the injection molding machine is provided with a plurality of temperature intervals, the temperature of each temperature interval is the same, the temperature is 190-195 ℃, and the nozzle temperature of the injection molding machine is 190-195 ℃.
Preferably, the inorganic compatilizer is nano calcium carbonate nano-CaCO3Or silicon carbide SiC.
Preferably, the chain extender is PCD or BDE.
Preferably, the plasticizer is DOP.
Preferably, the raw materials comprise 60 wt% of polylactic acid (PLA), 25 wt% of PBS and 25 wt% of compatilizer nano-CaCO310 wt%, chain extender PCD2 wt% and plasticizer DOP3 wt%.
Preferably, the twin-screw extruder in the step B has five heating intervals, and the temperatures of the heating intervals in the material extrusion direction are respectively 160 ℃, 170 ℃, 180 ℃, 185 ℃ and 185 ℃.
Preferably, the injection molding machine in the step C is provided with three temperature intervals, the temperature of each temperature interval is 195 ℃, and the temperature of the head of the injection molding machine is 195 ℃.
Preferably, the raw materials comprise, by weight, 65 wt% of polylactic acid (PLA), 20 wt% of PES, 9 wt% of compatilizer SiC, 3 wt% of chain extender PCD and 3 wt% of plasticizer DOP.
Preferably, the twin-screw extruder in the step B has five heating intervals, and the heating temperatures are 160 ℃, 170 ℃, 175 ℃, 180 ℃ and 185 ℃ respectively.
Preferably, the injection molding machine in the step C is provided with three temperature intervals, the temperature of each temperature interval is 190 ℃, and the temperature of the head of the injection molding machine is 190 ℃.
A packaging bag or a packaging box is made of the PLA material prepared by the preparation method, and has good toughness and hydrolysis resistance; meanwhile, the packaging box is made of degradable polylactic acid PLA and PBS or PES, so that the packaging bag/packaging box still has degradability and meets the environmental protection requirement.
Compared with the prior art, the invention has the beneficial effects that:
the toughness, mechanical strength and hydrolysis resistance of the obtained polylactic acid product are obviously improved, the actual application value of the polylactic acid PLA material is further improved, and the added PBS or PES is biodegradable plastic, so that the obtained PLA material still has biodegradable performance and meets the requirement of environmental protection.
Compared with other PLA modification methods, the method is simple and easy to implement and is more favorable for popularization and use.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a high-toughness hydrolysis-resistant PLA material comprises the following raw materials in parts by weight: the raw materials comprise 60% of polylactic acid PLA60 wt%, 25% of PBS25 wt% and a compatilizer nano-CaCO310 wt%, chain extender PCD2 wt%, plasticizer DOP3 wt%;
the preparation method comprises the following steps:
drying treatment of raw materials A:
drying polylactic acid PLA and PBS in an oven at 80 ℃ for 8h, exhausting gas in the oven every 4h, sealing the dried granules for later use,
inorganic compatilizer nano calcium carbonate nano-CaCO3Drying in a vacuum oven at 60 ℃ for 8h, exhausting in the oven every 4h, sealing the dried powder for later use,
drying the chain extender PCD in a vacuum oven at 40 ℃ for 8 hours, exhausting the air in the oven every 4 hours, and sealing the chain extender PCD for later use after drying;
b, preparation of a blending system:
60 wt% of polylactic acid PLA, 25 wt% of PBS and nano-CaCO serving as a compatilizer310 wt%, chain extender PCD2 wt% and plasticizer DOP3 wt% are compounded, a double-screw extruder is used for carrying out melt blending processing, the set rotating speed of the double-screw extruder is 75r/min, the double-screw extruder is provided with five heating intervals, the temperatures of the heating intervals along the material extrusion direction are respectively 160, 170, 180, 185 and 185 ℃, and the temperature of a discharging machine head of the double-screw extruder is 185 ℃;
c, injection molding: and (3) injection molding the melt-blended extruded melt by using an injection molding machine, wherein the injection molding machine is provided with three temperature intervals, the temperature of each temperature interval is equal to 195 ℃, and the nozzle temperature of the injection molding machine is 195 ℃.
A packaging box is made of the PLA material obtained by the preparation method, and has good toughness and hydrolysis resistance; meanwhile, the material of the packaging box is degradable, and meets the requirement of environmental protection.
Example 2
A preparation method of a high-toughness hydrolysis-resistant PLA material comprises the following raw materials in parts by weight: the raw materials comprise polylactic acid PLA65 wt%, PES20 wt%, compatilizer SiC9 wt%, chain extender PCD3 wt% and plasticizer DOP3 wt%.
The preparation method comprises the following steps:
drying treatment of raw materials A:
drying polylactic acid PLA and PES in an oven at 80 ℃ for 8h, exhausting gas in the oven every 4h, sealing the dried granules for later use,
drying the inorganic compatilizer silicon carbide SiC in a vacuum oven at 60 ℃ for 8 hours, exhausting the air in the oven every 4 hours, sealing the dried powder for later use,
drying the chain extender PCD in a vacuum oven at 40 ℃ for 8 hours, exhausting the air in the oven every 4 hours, and sealing the chain extender PCD for later use after drying;
b, preparation of a blending system:
compounding polylactic acid PLA60 wt%, PES20 wt%, a compatilizer SiC9 wt%, a chain extender PCD3 wt% and a plasticizer DOP3 wt%, and performing melt blending processing by using a double-screw extruder, wherein the set rotating speed of the double-screw extruder is 80r/min, the double-screw extruder is provided with five heating intervals, the temperatures of the heating intervals along the material extrusion direction are respectively 160 ℃, 170, 175, 180 and 185 ℃, and the temperature of a discharging machine head of the double-screw extruder is 185 ℃;
c, injection molding: and (2) injection molding the melt-blended extruded melt by using an injection molding machine, wherein the injection molding machine is provided with three temperature intervals, the temperature of each temperature interval is 190 ℃ in the same way, and the nozzle temperature of the injection molding machine is 190 ℃.
The embodiment only provides the use of one chain extender, and can also add PCD and BDE simultaneously for synergistic use so as to achieve the chain extension effect, thereby enhancing the toughness of the chain extender and inhibiting the chain breaking reaction of the PLA material in the hydrolysis process, and simultaneously can also effectively improve the thermal stability of the PLA, thereby playing the role of enhancing the hydrolysis resistance of the PLA material. .
In the invention, the addition of the flexible degradable plastic PBS or PES can also enhance the toughness of PLA and improve the tensile property and the impact resistance of the composite material, and because the crystallinity of PLA and PBS or PES are different, inorganic particle filler nano calcium carbonate or silicon carbide is required to be introduced to ensure that the PLA and the PBS or PES are better the same, so that the compatibility of the PLA and the PBS or PES is enhanced, and meanwhile, the nano calcium carbonate or silicon carbide is used as a filler for blending modification and has a certain toughening effect on polymers.
It should be noted that the illustrated embodiments of the present invention are only exemplary, and do not represent all embodiments, and the embodiments are for clearly explaining the present invention, and should not be construed as limiting the scope of the present invention, which is defined by the claims. Modifications, substitutions, or additions which may occur to those skilled in the art and which are within the teachings of the present invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of a high-toughness hydrolysis-resistant PLA material is characterized by comprising the following steps: the preparation method comprises the following raw materials in parts by weight: 60-65 parts of polylactic acid (PLA), 20-25 parts of at least one of flexible degradable plastics PBAT, PBS or PES, 8-10 parts of an inorganic compatilizer, 2-3 parts of a chain extender and 2-3 parts of a plasticizer;
the preparation method comprises the following steps:
drying treatment of raw materials A:
drying at least one of polylactic acid PLA and PBAT, PBS or PES in an oven at 70-80 ℃ for 8h, exhausting air once every 4h, sealing the dried granules for later use,
drying the inorganic compatilizer in a vacuum oven at 60 ℃ for 8 hours, exhausting air in the oven every 4 hours, sealing the dried powder for later use,
drying the chain extender in a vacuum oven at 40 ℃ for 8 hours, exhausting the air in the oven every 4 hours, and sealing for later use after drying;
b, preparation of a blending system:
compounding 60-65 parts of polylactic acid (PLA), 20-25 parts of PBS, 8-10 parts of an inorganic compatilizer, 2-3 parts of a chain extender and 2-3 parts of a plasticizer, and performing melt blending processing by using a double-screw extruder, wherein the set rotating speed of the double-screw extruder is 75-80r/min, the double-screw extruder is provided with a plurality of heating intervals, the temperature of the adjacent heating intervals is increased or leveled along the material extrusion direction, the temperature of the heating intervals is 160-185 ℃, and the temperature of a discharging machine head of the double-screw extruder is 185 ℃;
c, injection molding: and injection molding the melt-blended extruded melt by an injection molding machine, wherein the injection molding machine is provided with a plurality of temperature intervals, the temperature of each temperature interval is the same, the temperature is 190-195 ℃, and the nozzle temperature of the injection molding machine is 190-195 ℃.
2. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 1, wherein: the inorganic compatilizer is nano calcium carbonate nano-CaCO3Or silicon carbide SiC.
3. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 2, wherein: the chain extender is PCD or BDE.
4. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 3, wherein: the plasticizer is DOP.
5. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 4, wherein: the material comprises 60 weight portions of polylactic acid PLA, 25 weight portions of PBS and a compatilizer nano-CaCO310 parts of chain extender PCD2 parts and plasticizer DOP3 parts.
6. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 5, wherein: the double-screw extruder in the step B is provided with five heating intervals, and the temperatures of the heating intervals along the material extrusion direction are respectively 160 ℃, 170 ℃, 180 ℃, 185 ℃ and 185 ℃.
7. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 6, wherein: and C, arranging three temperature intervals in the injection molding machine in the step C, wherein the temperature of each temperature interval is 195 ℃, and the temperature of the machine head of the injection molding machine is 195 ℃.
8. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 4, wherein: the raw materials comprise, by weight, 65 parts of polylactic acid (PLA), 20 parts of PES, 9 parts of a compatilizer (SiC), 3 parts of a chain extender (PCD) and 3 parts of a plasticizer (DOP).
9. The process for preparing a high toughness hydrolysis resistant PLA material as claimed in claim 8, wherein: the double-screw extruder in the step B has five heating intervals, and the heating temperatures are respectively 160 ℃, 170 ℃, 175 ℃, 180 ℃ and 185 ℃.
10. A packing carton which characterized in that: the material of the packaging box is prepared by the preparation method of the high-toughness hydrolysis-resistant PLA material as claimed in any one of claims 1 to 11.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801445A (en) * | 2021-09-13 | 2021-12-17 | 苏州盛万达塑胶包装材料有限公司 | High-toughness heat-resistant degradable PLA material and preparation method thereof |
| CN115028974A (en) * | 2022-04-20 | 2022-09-09 | 深圳力越新材料有限公司 | Preparation method of PBS (Poly Butylene succinate) degradable environment-friendly material |
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| CN106633722A (en) * | 2016-11-21 | 2017-05-10 | 广州医科大学 | Anti-tearing biodegradable material with high toughness and preparation method of anti-tearing biodegradable material |
| CN107815072A (en) * | 2017-10-18 | 2018-03-20 | 福建恒安卫生材料有限公司 | A kind of biodegradable intermingling material of toughness reinforcing hydrolysis and preparation method thereof |
| CN111234481A (en) * | 2018-11-28 | 2020-06-05 | 南京科技职业学院 | Preparation method of high-toughness low-cost polylactic acid composite material |
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- 2020-12-30 CN CN202011614686.5A patent/CN112778721A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633722A (en) * | 2016-11-21 | 2017-05-10 | 广州医科大学 | Anti-tearing biodegradable material with high toughness and preparation method of anti-tearing biodegradable material |
| CN106519618A (en) * | 2016-11-23 | 2017-03-22 | 吉林中粮生化有限公司 | High-polylactic acid-content film and preparation method thereof |
| CN107815072A (en) * | 2017-10-18 | 2018-03-20 | 福建恒安卫生材料有限公司 | A kind of biodegradable intermingling material of toughness reinforcing hydrolysis and preparation method thereof |
| CN111234481A (en) * | 2018-11-28 | 2020-06-05 | 南京科技职业学院 | Preparation method of high-toughness low-cost polylactic acid composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801445A (en) * | 2021-09-13 | 2021-12-17 | 苏州盛万达塑胶包装材料有限公司 | High-toughness heat-resistant degradable PLA material and preparation method thereof |
| CN115028974A (en) * | 2022-04-20 | 2022-09-09 | 深圳力越新材料有限公司 | Preparation method of PBS (Poly Butylene succinate) degradable environment-friendly material |
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Application publication date: 20210511 |